A Transition-State Perspective of Proton-Coupled Electron Transfers

A Transition-State Perspective of Proton-Coupled Electron Transfers 

Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal 

Proton-Coupled Electron Transfer A Carrefour of Chemical Reactivity Traditions 

The energy contributions to the barrier of the PCET coming from independent changes in geometry that promote ET or PT can be expected to be additive. A physically meaningful model to describe PCET should be able to describe, with the same framework, the barriers of sequential PT and ET reactions in Mechanism (II), and also the barriers of HAT following 

Mechanism (I). In this chapter we merge the approaches of the Interacting/ Intersecting State Model (ISM) to atom and proton transfer reactions with treatment of electron transfer reactions by this same model. Transition-state energies and effective reaction frequencies are calculated and used to obtain the rate constants of representative CPET. 

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